Liquid hard surface cleaning compositions

ABSTRACT

LIQUID DETERGENT HARD SURFACE CLEANING COMPOSITIONS CONTAINING 0.25% TO 4% OF A WATER-SOLUBLE SYNTHETIC DETERGENT; 0% TO 6% OF A WATER-SOLUBLE BUILDER OR MIXTURE OF BUILDERS; 1% TO 10% OF AN ORGANIC SOLVENT OR MIXTURE OF SOLVENTS; 0.10% TO 0.5% OF A WATER-SOLUBLE CARBOXYMETHYLCELLULOSE HAVING A DEGREE OF SUBSTITUTION OF FROM ABOUT 1 TO ABOUT 2 AND A DEGREE OF POLYMERIZATION FROM ABOUT 1,000 TO ABOUT 3,000; AND WATER.

United States Patent O 3,591,509 LIQUID HARD SURFACE CLEANING COMPOSITIONS Lawrence Roy Parks and William Edward Zenk, Cincinnati, Ohio, assignors to The Procter & Gamble Company, Cincinnati, Ohio No Drawing. Filed Sept. 30, 1968, Ser. No. 763,948 Int. Cl. Clld 3/ 066 US. Cl. 252-437 6 Claims ABSTRACT OF THE DISCLOSURE Liquid detergent hard surface cleaning compositions containing 0.25% to 4% of a water-soluble synthetic detergent; to 6% of a water-soluble builder or mixture of builders; 1% to of an organic solvent or mixture of solvents; 0.10% to 0.5% of a water-soluble carboxymethylcellulose having a degree of substitution of from about 1 to about 2 and a degree of polymerization from about 1,000 to about 3,000; and water.

BACKGROUND OF THE INVENTION This invention relates to liquid detergent compositions. More particularly, this invention relates to liquid detergent compositions suitable for hard surface cleaning in a no-rinse method with improved cleaning and without the usual resulting filming or streaking problem.

In general, liquid detergent compositions are well known in the art and many such compositions have been used in the past for cleaning hard surfaces such as glass, painted walls, woodwork and the like. Generally when such compositions are applied to the above surfaces without a subsequent rinse, they leave a film after their cleaning function has been performed. This residual film, when it contains an organic detergent, can act almost as a trap and collects dirt. The surface thus cleaned with such a composition does not appear clean and can become dirty again even more rapidly than the same surface would become dirty in the absence of the residual film.

Many attempts have been made to produce a so-called volatile detergent composition. Theoretically, such a volatile composition when applied to a surface would perform its cleaning function and then completely evaporate, leaving the clean surface free of any residual film which would enhance the subsequent collection of dirt or soil. Volatile compositions have been prepared in the past which will substantially evaporate after use leaving the surface devoid of any noticeable residual film but, in general, such detergent compositions will not adequately or sufficiently clean the surface as desired or present other negatives such as inflammability or noxious odor.

One of the principal objects of the present invention is to provide a novel liquid detergent composition which effectively cleans hard surfaces when used in a no-rinse method without leaving an objectionable residual film.

It is a further object of the present invention to provide liquid detergent hard surface cleaner compositions containing specific carboxymethylcelluloses in small amounts which aid the composition in staying in place when sprayed on vertical surfaces until the composition and any dirt on the surface can be wiped off.

Other objects and advantages of the present invention will be readily apparent to one skilled in the art from the following description.

SUMMARY OF THE INVENTION The objects of the present invention are achieved by a liquid detergent composition consisting essentially of an aqueous medium containing a synthetic detergent; a

builder or combination of builders; an organic solvent or mixture of organic solvents which are sufficiently hydrophobic to dissolve oily soils, e.g., grease and carboxymethylcelluloses having a high degree of substitution and degree of polymerization.

The present invention consists of a novel liquid detergent composition consisting essentially of from about 0.25% to about 4.0% by weight of a compatible watersoluble synthetic detergent; from about 0% to about 6.0% by weight of a water-soluble detergency builder, e.g., a builder selected from the group consisting of watersoluble polyphosphonates, tripolyphosphates, orthophosphates, pyrophosphates and aminopolycarboxylates and mixtures thereof; from about 1.0% to about 10.0% by weight of an organic solvent or mixture of solvents of the general formula wherein R is a straight chain alkyl group containing from about 1 to about 4 carbon atoms, R is selected from the group consisting of H and CH and n is an integer of from 1 to about 3; from about 0.10% to about 0.5% of a water-soluble carboxymethylcelluose having a degree of substitution of from about 1 to about 2 and a degree of polymerization of from about 1,000 to about 3,000.

Among the detergents which have been found useful as the active detergent agent in the compositions of the present invention and which are clearly within the contemplation of this invention are the following examples:

(A) Anionic synthetic detergents: This class of synthetic detergents includes alkali metal, ammonium and substituted ammonium salts of organic sulfuric reaction products having in their molecular structure an alkyl radical, either straight chain or branched chain, containing from about 8 to about 18 carbon atoms, preferably from about 10 to about 14 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. Important examples of the synthetic detergents which form a part of the preferred compositions of the present invention are the following anionic detergents as the alkali metal (e.g., sodium and potassium), ammonium and substituted ammonium (e.g., lower alkanol ammonium) salts: alkyl sulfates, especially those containing from about 8 to about 12 carbon atoms and those obtained by sulfating the higher alcohols produced by reducing the glycerides of coconut oil, linear alkylbenzene sulfonates in which the alkyl radical contains from about 6 to about 18 carbon atoms, especially those containing from about 6 to about 8 carbon atoms, and from about 10 to about 14 carbon atoms; sulfuric acid esters of polyhydric alcohols incompletely esterified with higher fatty acids; higher fatty acid esters of low molecular weight alkanol sulfonic acids; higher fatty acid ethanolamide sulfates; higher fatty acid amides of amino alkyl sulfonic acids; sulfated reaction products of long chain alcohols containing from about 8 to about 18 carbon atoms with from 1 to about 15 moles of ethylene oxide per mole of alcohol, especially those sulfated reaction products of C to C alcohols with about 3 moles of ethylene oxide per mole of alcohol; alkyl sulfonates wherein the alkyl group contains from about 8 to about 18 carbon atoms; and the novel water-soluble salts of C -C sulfonated olefins of US. Pat. 3,332,880, issued July 25, 1967, to Kessler et a1, especially the C sulfonated olefin.

(B) Nonionic synthetic detergents: This class of synthetic detergents may be broadly defined as compounds, aliphatic or alkyl aromatic in nature which do not ionize in water solution.

For example, a well known class of nonionic synthetic detergents is made available on the market under the trade name of Pluronic. These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of the molecule which, of course, exhibits water insolubility has a molecular weight of from about 1200 to 2500. The addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the Water solubility of the molecule as a whole and the liquid character of the product is retained up to the point where polyoxyethylene content is about 50% of the total weight of the condensation product.

Other suitable nonionic synthetic detergents include:

(1) The polyethylene oxide condensates of alkylpnenols, e.g., the condensation products of alkylphenols or dialkylphenols wherein the alkyl group contains from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to to moles of ethylene oxide per mole of alkylphenol. The alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, n-octene, or n-nonene, for example.

(2) Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. For example, compounds containing from about to about 80% polyoxyethylene by weight and having a molecular weight of from about 5000 to about 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylenediamine and excess propylene oxide, said base having a molecular weight of the order of 2500 to 3000, are satisfactory.

1(3) The condensation product of aliphatic alcohols having from about 6 to about 18 carbon atoms, and especially from about 8 to about 10 carbon atoms in a straight chain configuration with ethylene oxide, e.g., from 6 to 30 moles of ethylene oxide per mole of alcohol. Specific examples suitable for use in this invention include a decyl alcohol/ ethylene oxide condensate containing an average of 9 moles of ethylene oxide per mole of decyl alcohol and a coconut alcohol ethylene oxide condensate containing an average of 20 moles of ethylene oxide per mole of alcohol.

(4) Long chain tertiary amine oxides corresponding to the following general formula, RRRN O wherein R is an alkyl, alkenyl or monohydroxyalkyl radical ranging from 8 to 18 carbon atoms in chain length and R and R are each alkyl or monohydroxyalkyl groups containr amine oxide, dimethyldecylarnine oxide, dimethyltetradecylamine oxide, dimethylhexadecylamine oxide;

(5) Long chain tertiary phosphine oxides corresponding to the following general formula RRR"P O wherein R is an alkyl, alkenyl or monohydroxyalkyl radical ranging from 8 to 18 carbon atoms in chain length, and R and R" are each alkyl or monohydroxyalkyl groups containing from 1 to 3 carbon atoms. The arrow in the formula is a conventional representation of a semi-polar bond. Examples of suitable phosphine oxides are: dimethyloctylphosphine oxide, dimethyldecylphosphine oxide, dimethyldodecylphosphine oxide, dimethyltetradecylphosphine oxide, ethylmethyltetradecylphosphine oxide, cetyldimethylphosphine oxide, dimethylstearylphosphine oxide, cetylethylpropylphosphine oxide, diethyldodecylphosphine oxide, diethyltetradecylphosphine oxide, dipropyldodecylphosphine oxide, bis (hydroxymethyl)dodecylphosphine oxide, bis-(2-hydroxyethyl)dodecylphosphine oxide, (2-hydroxypropyl)methyltetradecylphosphine oxide, dimethyloleylphosphine oxide, and dimethyl-(2-hydroxydodecyl)phosphine oxide; and

R1CN(R?)2 wherein R contains from about 6 to about 18 carbon atoms and R is selected from the group consisting of H, CH OH, CH CH OH, CH CH CH OH and CH CH(CH )OH (C) Zwitterionic synthetic detergents: This class of synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium compounds, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms, preferably from about 10 to about 14 carbon atoms and one contains an anionic Water solubilizing group, e.g., carboxy, sulfo or sulfato. Examples of the preferred compounds falling within this definition are described in German Pat. 1,018,421 and US. Pats. 2,082,275, 2,702,279 and 2,255,082. A specific preferred example is 3- (N,N'-dimethyl-N-decylammonio 2-hydroxypropane-l-sulfonate. When the solvent is either propylene glycol butoxy ether, propylene glycol isobutoxy ether, dipropylene glycol butoxy ether or mixtures thereof. Another preferred example is 3-(N,N'-dimethyl-N- decylammonio) propane-l-sulfonate wherein coconutalkyl has the following chain length distribution: 2% C 66% C 23% C and 9% C and 3-(N,N-dimethyl-N-alkylammonio 2-hydroxy-propanel-sulfonate wherein the alkyl group has an average chain length Of C10.

The anionic, nonionic and Zwitterionic detergents mentioned above can be used singly or in combination in the practice of the present invention. The synthetic detergent comprises from about 0.25% to about 4.0% by weight of the total composition. If more than about 4.0% is used an undesired streaking and filming problem results and if less than about 0.25% is used the desired level of cleaning will not be achieved. A preferred range of from about 0.50% to about 2.0% by weight of a synthetic detergent as described above will yield the best results of the invention.

Preferred detergent compositions are disclosed in the copending application of Harry J. Aubert and James A. Hellyer, Ser. No. 683,111, filed Nov. 15, 1967, entitled Liquid Hard Surface Cleaning Compositions and the copending applications of William E. Zenk entitled Liquid Hard Surface Cleaning Compositions filed concurrently herewith, Ser. No. 763,949 filed, Sept. 30. 1968.

The builders which can be utilized in the practice of the invention to give the desired cleaning performance without attendant excessive filming and streaking problems are selected from the group consisting of water-soluble polymeric carboxylates, polyphosphonates, tripolyphosphates, orthophosphates, borates, pyrophosphates, and amino polycarboxylates.

Suitable builders include the alkali metal (e.g., sodium and potassium) and ammonium (including substituted ammoniums, e.g., triethanolammonium) amino polycarboxylates, organic polyphosphonates, polymeric carboxylates, pyrophosphates, orthophosphates, and tripolyphosphates. Suitable amino polycarboxylates are those described in US. Pat. 3,329,617 and 3,336,233. Suitable polyphosphonates are those described in US. Pat. 3,329,617; 3,336,233; 3,332,880; 3,213,030; 3,400,148, 3,400,176; and 3,400,151; and copending US. applications: Roy, Ser. No. 266,055, filed Mar. 18, 1963; Roy, Ser. No. 493,925, filed Mar. 18, 1963; Quimby, Ser. No. 517,073, filed Dec. 28, 1965; Quimby and Prentice, Ser. No. 587,417, filed Oct. 18, 1966; Quimby, Ser. No. 605,606, filed Dec. 29, 1966; Curry, Ser. No. 717,999, filed Apr. 1, 1968; Nicholson and Campbell, Ser. No. 694,002, filed Dec. 27, 1967; Nicholson and Campbell, Ser. No. 694,003, filed Dec. 27, 1967; and Prentice and Quimby, Ser. No. 694,106, filed Dec. 28, 1967. Suitable polymeric carboxylates are disclosed in US. Pat. 3,308,067. All of the above patents and applications are incorporated herein by reference. Preferred builders are sodium nitrilotriacetate, potassium pyrophosphate, potassium tripolyphosphate and sodium or potassium ethanel-hydroxy-l,l-diphosphonate and its derivatives.

A preferred mixture of builders is the combination of a water-soluble ethane-l-hydroxy-1,1-diphosphonate and water-soluble nitrilotriacetate, preferably the sodium salts.

Other suitable builders are disclosed hereinafter in the examples.

The builder or builder mixture comprises from about 0 to about 6% by weight of the total composition if more than about 6% by weight is used, then an undesired filming and streaking problem is observed. If less than about 1% by weight is used the builder will not be able to contribute to the desired cleaning results of the invention. If about 1.5% to 2.5% builder by weight of the total composition is used the best cleaning and non-filming results of the invention are achieved.

The solvents which can be used, either alone or in combination, in the practice of this invention to aid in grease removal are of the general formula:

RI R''(O CHZ OH)uOH wherein R is a straight chain alkyl group containing from about 1 to about 4 carbon atoms, R is selected from the group consisting of H and CH and n is from 1 to about 3.

The solvent or solvent mixture of this invention comprises from about 1% to about by weight of the total composition. If more than about 10% by weight is used, the resulting solvent based cleaner is undesirably capable of removing paint and finishes from the surfaces it is used on. Furthermore, such large amounts of solvents present an odor problem. If less than about 1% by weight is used, then the desired cleaning function is not adequately performed. A preferred range of solvent is from about 4% to about 8% by weight.

When certain solvents within the general formula above are used, e.g., propylene glycol butoxy ether, propylene glycol isobutoxy ether, dipropylene glycol butoxy ether, mixtures thereof, etc., a hydrotrope can be employed to insure complete solubility. Among the hydrotropes that can be utilized are sodium, potassium and ammonium toluene sulfonates, xylene sulfonates, and cumene sulfonates in an amount ranging from .5% to 3.0% of the composition.

When propylene glycol butoxy ether, propylene glycol isobutoxy ether, dipropylene glycol butoxy ether, mixtures thereof, etc. are used as the solvent, care must be taken in selecting a compatible detergent, e.g., the alkali metal (e.g., sodium and potassium), ammonium and substituted ammonium (e.g., lower alkanol ammonium) hexyl, octyl, nonyl, decyl, undecyl and dodecyl sulfates; linear alkylbenzene sulfonates in which the alkyl radical contains from about 6 to about 8 carbon atoms, 3-[N,N- dimethyl N decylammonio]-2-hydroxypropane-l-sulfonate, and 2-(N,N,N"-trimethylammonio)decanoate, in order to achieve the desired results of the present invention.

When many of the above compositions are sprayed onto a vertical wall either with a mechanical sprayer or an aerosol, they tend to run down the surface before they can be wiped off. This tendency is undesirable since it can spread the stain and require excessive wiping. It has been discovered that the addition of from about 0.10% to about 0.5% of a water-soluble (e.g. sodium, potassium, ammonium, or triethanolammonium) carboxymethylcellulose having a degree of substitution of from about 1 to about 2 and a degree of polymerization of from about 1,000 to about 3,000 to the above described compositions will improve the ability of the compositions to hold on vertical surfaces when sprayed onto said vertical surfaces from a mechanical sprayer or aerosol. The carboxymethylcellulose is compatible with the compositions and can easilybe dissolved in them to prepare a single phase system. Carboxymethylcelluloses having lower degrees of polymerization will not be sufficiently effective. Amounts of the preferred carboxymethylcellulose in excess of about 0.5 tend to adversely affect the spray pattern so that the surface is covered incompletely. When no builder is used, the level of carboxymethylcellulose should be at least about 0.35% and preferably about 0.4% Within the limits set forth herein, the composition will have a good spray pattern when sprayed onto a vertical surface and will remain for a sufficient time to permit the user to wipe the surface clean.

Miscellaneous materials such as coloring agents, aerosol propellants, perfumes, sodium borate decahydrate (borax) as a pH buffer, and other materials which are well known as constituents in liquid detergent compositions and which are compatible in the formulations of the present invention can also be present in minor amounts.

The various constituents of the liquid detergent compositions of the present invention can be admixed in any sequence to achieve the desired objects as stated above. It is preferred, however, for ease of solubility, to add the components in the following order at temperatures of between about 40 F. and about F. with constant agitation: water, builder, solvents, detergent and, if any, the optional components.

The liquid detergent compositions of this invention can be utilized either full strength or in dilute solutions. A preferred method of application is in the form of a spray or aerosol for small spots and for small spot cleaning, full strength is recommended. When one wishes to apply the compositions over large surfaces utilizing a sponge, mop, or brush, then dilution is suggested although such is up to the individual situations requirements.

The following examples illustrate in detail the manner in which the invention can be practiced. However, the invention is not confined to the specific limitations set forth in the individual examples but, rather, to the scope of the appended claims.

PREFERRED EMBODIMENTS Example I A liquid detergent composition was prepared from the following ingredients:

Percent Sodium linear alkyl benzene sulfonate (alkyl chain length averaging 11 carbon atoms) 2.0 'Diethylene glycol n-butyl ether 4.0 Ethylene glycol n-butyl ether 2.0 Trisodium salt of nitrilotriacetic acid monohydrate 1.0

Ethane 1 hydroxy-l,1-diphosphonic acid 0.76

Sodium carboxymethylcellulose (D.P. 1,000;

D.S.-l.2) 0.25 Perfume 0.35 Sodium hydroxide 0.7 Soft water Balance to 100 This composition was a stable liquid composition with a pH of about 12. At this pH in the composition of this Example I and succeeding examples, the diphosphonic acid is neutralized to the tetra sodium salt by the sodium hydroxide. This composition, when sprayed on a vertical surface, gives a good pattern and does not run down immediately, enabling the user to wipe the surface clean.

Substantially the same results in cleaning vertical surfaces without the product running down are obtained with the compositions of Example I when any of the following surfactants are substituted on an equal weight basis for the sodium linear alkyl benzene sulfonate in Example I, (coconut as used below has the following chain length distribution: 2% C 66% C 23% C and 9% C 7 (1) Sodium, potassium, ammonium and substituted ammonium (a) alkyl sulfates wherein the alkyl is derived from coconut oil;

(b) alkyl sulfonates prepared by sulfonating alpha olefins containing an average of about 12 carbon atoms;

(c) alkyl benzene sulfonates containing alkyl chains containing an average of about 11 carbon atoms;

(d) fatty acyl isethionates wherein the fatty acyl groups are derived from coconut oil;

(e) fatty alcohol ethylene oxide sulfates wherein the alcohol radical is derived from coconut, and where there are about 3 moles of ethylene oxide per mole of fatty alcohol;

(f) N-coconut fatty acyl taurides;

(g) coconut fatty acid monoglyceride sulfates;

(h) coconut fatty acid diethanolamide sulfates;

(i) coconut fatty acid diethanolamides;

(j) olefin sulfonates obtained from the S sulfonation of dodecene;

(k) octyl sulfates;

(l) decyl sulfates;

(m) hexylbenzene sulfonates;

(n) octylbenzene sulfonates;

(o) heptylbenzene sulfonates;

(p) nonyl sulfates;

(q) olefin sulfonates obtained by sulfonating tetradecene with 50;, and

(r) random octylbenzene sulfonates.

(a) the condensation product of ethylene oxide with a condensation product of propylene oxide and propylene glycol, the ethylene oxide constituting 50% of the total weight of the condensation product and the total molecular weight of the condensation product being about 3600;

(b) the condensation product of ethylene oxide with a condensation product of propylene oxide and ethylene diamine, the ethylene oxide constituting 50% of the total weight of the condensation product and the total molecular weight of the condensation product being about 7500;

(0) alkyl phenol ethylene oxide reaction product wherein the alkyl group contains about 12 carbon atoms and there are approximately moles of ethylene oxide per mole of alkyl phenol; the condensation product of one mole of alcohol derived from coconut oil and about 10 moles of ethylene oxide.

(d) decyldimethylamine oxide;

(e) decyldimethylphosphine oxide;

(f) 3 (N,N dimethyl N-decylammonio)-2-hydroxypropane-l-sulfonate;

(g) 3 (N,N dimethyl N coconutalkylammonio)-2- hydroxy-propane-l-sulfonate; and

mixtures thereof.

Example II The following liquid detergent composition is prepared.

Percent Sodium linear alkyl benzene sulfonate (alkyl chain length averaging 7 carbon atoms) 2.0 Diethylene glycol n-butyl ether 4.0 Ethylene glycol n-butyl ether 2.0 Ethane-l-hydroxy-1,1-diphosphonic acid 1.5 Perfume .35

Potassium carboxymethylcellulose (D.P.2,400;

D.S.1.2) 0.25 Sodium hydroxide 1.5 Soft water Balance to 100 The composition is a stable liquid composition with a pH of 12. When the composition is sprayed on smooth vertical surfaces a desired level of cleaning is obtained without the product running down the surface.

Example III The following liquid detergent composition is prepared.

Percent Sodium decyl sulfate 2.0 2-hydroxy-3-butoxypropane(Propasol B) 6.0

Ethane-1-hydroxy-1,l-diphosphonic acid 0.76

Trisodium salt of nitrilotriacetic acid monohydrate 1.0 Potassium cumene sulfonate 2.0 Sodium carboxymethylcellulose (DP-2,000; D.S.

1.6) .2 Perfume .35 Sodium hydroxide .7 Soft water Balance to 10 The composition is a stable liquid composition with a pH of 12. When this composition is sprayed on smooth vertical panels a desirable level of cleaning is achieved without any significant running of the formula.

Example IV The following liquid detergent composition is prepared:

Percent 3(N-N-dimethyl-N-decyl alkylammonio) 2 hydroxypropane-l-sulfonate 2-hydroxy-3-butoxypropane This composition is a stable liquid composition with a pH of about 12. When sprayed on smooth vertical surfaces, this composition cleans well without significant running.

The following table shows the comparison of different chain length sodium alkyl sulfates.

Coconut 1 010 Ca Ca Cleaning Basis Equal... Equal Equal. Filming Lig tmoderate... Light... Trace, light...

Coconut; refers to the following chain length distribution: 2% C1 66% C 23% C14; and 9% C10. 0 alkyl sulfate is preferred and Cs and Cs alkyl sulfates are next best.

Similar tests with 3-[N,N-dimethyl-N-decylammonio]- 2-hydroxypropane 1 sulfonate (C HAPS) and ammonium coconut 1 alkyl polyethoxylate (3 moles) (NH AE S) gave the following results.

Sodium octylbenzene CmI-IAPS CHHAPS NH4AE S sulfonate Cleaning Equal Worse Basis. Filming Trace, light--- Heavy Light, Light.

moderate.

Similar results are obtained when 1% detergent is used instead of 2%.

The C HAPS formula did not immediately run down when sprayed from a mechanical sprayer onto a vertical surface.

1 See footnote in table immediately above.

Example IV The following compositions all have the general formula:

10 substitution of from about 1 to about 2 and a degree of polymerization of from about 1000 to about 3000; and (E) the balance water.

Percent 2. The composition of claim 1 wherein the water- Water soluble synthetic detergent 2-0 soluble synthetic detergent is sodium linear alkylbenzene Propylene glycol sobutoxy ether 3.0 sulfonate wherein the alkyl group contains from about Dipropylene glycol butoxy ether 3.0 6 to about 8 carbon atoms. Builder 2-0 3. The composition of claim 1 wherein the builder is Sodium carboxymethyl cellulose (DR 2,000; D3. sodium ethane-1-hydroxy-1,l-diphosphonate.

1.4) 0.3 4. The composition of claim 1 wherein the builder is Hydrotrope 2.0 a mixture of sodium ethane-l-hydroxy-l,l-diphosphonate Water Balance and sodium nitrilotriacetate.

Composition Detergent Builder Hydrotrope 1 Potassium hexylbenzene sulfonate Sodium tripolyphosphate Sodium toluene sulfonate. 2 Sodium octylbenzeue sulfonate Potassium ethane-1,1,2-triphosphonate Potassium toluene sulfonate 3 Ammonium nonylbenzene sulfonate Tnethanolammonium poly(itaconate-acry- Ammonium toluene sulfonate,

late) (4:1 on a molar basis) (specific viscosity of 1% by Weight, in dimethyl formamide at room temperature, .40) (equivalent weight, 65.8). 4 Potassium hexylbenzene sulfonate Potgssiutm ethane-l-hydroxy-l,1,2-triphos- Sodium xylene sulfonate.

p ona e. 5 Sodium r-octylbenzene sulfonate Am nonizum ethane-2-hydroxy-1,1,2-triphos- Potassium xyl ne sulfonate, p ona e. 6 Sodium r-hexylbenzene sulfouate Trigotastsium ethane-1-hydroxy-1,l-diphos- Ammonium xylene sulfonate. D one 6. 7 Potassium nonyl sulfate Sodium nitn'lotriacetate Sodium benzene sulfonate. 8 Sodium 4-nonyl sulfate Potassium pyrophosphate Potassium benzene sulfonate. 9 Sodium olefin sulionate Ammonium methylene-diphosphonat Ammonium benzene sulfonate. 10 Potassium salt oi the detergent of Oomposi- Sodium ethylene-1,1diphosphonate Sodium cumene sulfonate.

ion 9. 11 Sodium nonyl polyethoxlate (4 moles) sul- Sodium N-(2-hydroxy-ethyl)-ethylenedia- Potassium cumene sulionate.

fate. Iniuetriacetate. Potassium deeyl polyethoxylate (2 moles) Potassium N-(2-hydroxyethyl-nitrilodiace- Triethanolammonium cumeue sulfonate.

su a e. a es. Sodium decyl sulfate Potassium isopropylidene diphosphonate. Triethanolammonium benzene sulfonate. Potassium undecyl sulfate Ammonium ethylidene diphosphonate Triethanolammonium xylene sulfonate. Potassium trideoyl sulfate Potassium hydroxymethanediphosphonate. Triethanolammonium toluene sulfonate, 16 1:1 mixture by weight of sodium hexylben- 1:1 mixture by weight of ammonium pro- Morpholinium cumene sulfonate.

zene sulfonate and sodium octyl sulfate.

pane'l,1,3,3-tetraphosphonate and ammotnium propane-1,2,2,3-tetraphosphono 6. 17 1:1 mixture by weight of sodium octylben- Ammoni m propane-1,l,2,3-tetraphospho- Morpholinium xylene sulionate,

zene sulfonate and sodium decyl sulfate. nate. 1s 3-[N,N-dimethyl-N-deeylammonio]-2-hy- 1:1 mxture by weight of sodium carbonyL Morpholinium toluene sulfonate,

droxypropane-l-sulionate. diphostphonate and sodium hexametaphosp one 8. 19 do Sodium orthophosphate Sodium cumene sulionate.

In addition to the preferred embodiments described herein, other arrangements and variations within the spirit and scope of the invention and the appended claims will occur to those skilled in the art.

What is claimed is:

*1. A novel liquid detergent hard surface no-rinse cleaning composition consisting essentially of:

(A) from about 0.25% to about 4.0% by weight of a compatible short chain water-soluble synthetic detergent selected from the group consisting of: (1) 3(-N,N'-dimethy1 N decy1ammonio)-2-hydroxypropane 1 sulfonate, (2) 2(N,N',N"-trimethylammonio) decanoate, (3) and alkali metal straight chain alkylbenzene sulfonates wherein said alkyl group contains from about 6 to about 8 carbon atoms,

(B) from about 1% to about 6.0% by weight of a water-soluble detergency builder selected from the group consisting of water-soluble polyphosphonates, tripolyphosphonates, orthophosphates, borates, pyrophosphates, polymeric carboxylates, and amino polycarboxylates and mixtures thereof;

(C) from about 1.0% to about 10% by weight 01 an organic solvent or mixture of solvents selected from the group consisting of propylene glycol butoxy ether, propylene glycol isobutoxy ether, and dipropyleneglycol butoxy ether, and mixtures thereof;

(D) from about 0.1% to about 0.5% of a watersoluble carboxymethylcellulose having a degree of 5. The composition of claim 1 wherein the builder is sodium orthophosphate.

6. The composition of claim 1 containing no builder and at least about 0.35% carboxymethylcellulose.

FOREIGN PATENTS 730,279 5/1955 Great Britain 252-153 LEON D. ROSDOL, Primary Examiner P. E. WILLIS, Assistant Examiner U.S. C1.X.R.

Patent No. 3,591,509 Da July 6, 1971 Inventor(s) Lawrence Roy Parks and William Edward Zenk It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

At column 2, line 25, "carboxymethylcelluose should read carboxymethylcellulose In Example 4, column 8, line 31, "nitriloacetic" should read nitrilotriacetic In claim 1, column 9, line 65, "tripolyphosphonates" should read tripolyphosphates Signed and sealed this I 8th day of January 1 972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GO'I'TSGHALK Attesting Officer Acting Commissioner of Patents 

